Iridium pincer complex for alkane dehydrogenation process

ABSTRACT

Disclosed herein are processes for dehydrogenation of an alkane to an alkene using an iridium pincer complex and iridium pincer complexes. In the dehydrogenation reactions, hydrogen that is co-formed during the process must be removed for the chemical reaction to proceed and to prevent the excess hydrogen from poisoning the catalyst. In one embodiment the process comprises providing an alkane feedstock comprising at least one alkane and contacting the alkane with an iridium pincer complex in the presence of a hydrogen acceptor selected from the group consisting of ethylene, propene, or mixtures to form an alkene product. The processes disclosed herein can accomplish facile, low-temperature transfer dehydrogenation of alkanes with unprecedented selectivities and TONs at a reasonable rate of conversion

This application is a Divisional of U.S. application Ser. No. 14/638,997filed Mar. 4, 2015 entitled “Alkane Dehydrogenation Process” whichclaims priority to U.S. Provisional No. 61/947,915 filed Mar. 4, 2014entitled “Alkane Dehydrogenation Process”, the contents of both of whichare herein incorporated by reference in their entireties.

FIELD OF ART

Provided is a process for generating olefins (i.e., alkenes) fromalkanes. More specifically, the process uses iridium pincer complexcatalysts for generating olefins from alkanes.

BACKGROUND

Olefins are an important and versatile feedstock for fuels andchemicals, but they are not as widely available naturally as alkanes.The chemical industry uses olefins as intermediates in a variety ofprocesses. The largest chemical use is linear α-olefins used in theformation of polyolefins such as ethylene-1-octene copolymers. Also andmost importantly, low carbon number olefins have the potential to beconverted into higher carbon number molecules that would be suitable forfuels, particularly, diesel. Other products formed from olefins includesurfactants, lubricants, and plasticizers. Thus, the direct productionof alkenes from alkanes via dehydrogenation has drawn great attention.Many heterogeneous catalysts are known to effect dehydrogenation at hightemperatures (ca. 500-900° C.), but applications are limited to simplemolecules such as ethane or ethylbenzene due to the low selectivity ofthese catalyst systems. In the case of higher alkanes, lack ofselectivity (including catalyst-deactivating coking) severely impactsthe utility of dehydrogenation.

Many iridium complexes as catalysts are known. During the 1980s, it wasdiscovered that certain iridium complexes are capable of catalyticallydehydrogenating alkanes to alkenes under thermal and photolyticconditions (see, e.g., J. Am. Chem. Soc. 104 (1982) 107; 109 (1987)8025; 1 Chem. Soc., Chem. Commun. (1985) 1829). For a more recentexample, see Organometallics 15 (1996) 1532.

Pincer ligand complexes of rhodium and iridium as catalysts for thedehydrogenation of alkanes are receiving widespread attention. See, forexample, F. Liu, E. Pak, B. Singh, C. M. Jensen and A. S. Goldman,“Dehydrogenation of n-Alkanes Catalyzed by Iridium “Pincer” Complexes:Regioselective Formation of a-olefins,” J. Am. Chem. Soc. 1999, 121,4086-4087; F. Liu and A. S. Goldman, “Efficient thermochemical alkanedehydrogenation and isomerization catalyzed by an iridium pincercomplex,” Chem. Comm. 1999, 655-656; and C. M. Jensen, “Iridium PCPpincer complexes: highly active and robust catalysts for novelhomogenous aliphatic dehydrogenations,” Chem. Comm. 1999, 2443-2449. Theuse of compounds such as (PCP)MH₂ (PCP═C₆H₃(CH₂PBut₂)₂-2,6) (M=Rh, Ir)dehydrogenate various cycloalkanes to cycloalkenes with turnovers of70-80 turnovers/hour.

Various pincer catalysts supported on solid supports via polar anchoringgroups are also known. See Huang, Z.; Brookhart, M.; Goldman, A. S.;Kundu, S.; Ray, A.; Scott, S. L.; Vicente, B. C. Adv. Synth. Catal.2009, 351, 188 and Huang, Z.; Rolfe, E.; Carson, E. C.; Brookhart, M.;Goldman, A. S.; El-Khalafy, S. H.; MacArthur, A. H. R. Adv. Synth.Catal. 2010, 352, 125.

In addition, “pincer” complexes of platinum-group metals have been knownsince the late 1970s (see, e.g., J. Chem. Soc., Dalton Trans. (1976)1020). Pincer complexes have a metal center and a pincer skeleton. Thepincer skeleton is a tridentate ligand that generally coordinates withthe meridional geometry. The use of pincer complexes in organicsynthesis, including their use as alkane dehydrogenation catalysts, wasdeveloped during the 1990s and is the subject of two review articles(see Angew. Chem. Int. Ed. 40 (2001) 3751 and Tetrahedron 59 (2003)).See also U.S. Pat. No. 5,780,701. Jensen et al. (Chem. Commun. 1997 461)used iridium pincer complexes to dehydrogenate ethylbenzene to styrene.Recently, additional pincer complexes have been developed thatdehydrogenate hydrocarbons. For some recent examples, see J. Mol. Catal.A 189 (2002) 95, 111 and Chem. Commun. (1999) 2443.

Initial attempts to design effective homogeneous catalytic systems foralkane dehydrogenation were hampered by catalyst decomposition. Insubsequent attempts, Kaska and Jensen reported the first ever robustsystem for catalytic transfer dehydrogenation of alkanes that was basedon a pincer-ligated iridium complex (^(tBu4)PCP)Ir(H₂). (See, Gupta, M.,Hagen, C., Flesher, R. Chem. Commun. 1996, 36, 2083-2084 and Gupta, M.;Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. M.; Barbara, S. J.Am. Chem. Soc. 1997, 267, 840-841.) Later it was observed that both(^(tBu4)PCP)Ir(H₂) and its isopropyl analog (^(iPr4)PCP)Ir(H₄) werefound to selectively activate C—H bond of alkanes. (See, Liu, F., Pak,E. B., Singh, B., Jensen, C. M., Goldman, A. S. J. Am. Chem. Soc. 1999,121, 4086-4087.) These catalysts were also effective for theacceptorless dehydrogenation of alkanes. (See, Xu, W., Rosini, G. P.,Krogh-Jespersen, K., Goldman, A. S., Gupta, M.; Jensen, C. M.; Kaska, W.C. Chem. Commun. 1997, 2273-2274; and Liu, F.; Goldman, A. S. Chem.Commun. 1999, 655-656; and Krogh-Jespersen, K.; Czerw, M.; Summa, N.;Renkema, K. B.; Achord, P. D.; Goldman, A. S. J. Am. Chem. Soc. 2002,124, 11404-16.) These studies paved the way for design of several pincerbased catalytic systems for alkane dehydrogenation reactions and theirmechanistic studies. (See, Renkema, K. B.; Kissin, Y. V; Goldman, A. S.J. Am. Chem. Soc. 2003, 125, 7770-1; and Choi, J.; MacArthur, A. H. R.;Brookhart, M.; Goldman, A. S. Chem. Rev. 2011, 111, 1761-79; andHaibach, M. C.; Kundu, S.; Brookhart, M.; Goldman, A. S. Acc. chem. res.2012, 45, 947-58.) Over the years many research groups have reportedvariants of (^(tBu4)PCP)Ir(H₂) and (^(iPr4)PCP)Ir(H₄) where either thesubstituent at the para position of the aryl group has been altered (seeZhu, K.; Achord, P. D.; Zhang, X.; Krogh-Jespersen, K.; Goldman, A. S.J. Am. Chem. Soc. 2004, 126, 13044-53; and Huang, Z.; Brookhart, M.;Goldman, A. S.; Kundu, S.; Ray, A.; Scott, S. L.; Vicente, B. C. Adv.Synth. Catal. 2009, 351, 188-206) or the CH₂ linkers have been modified.(See, Göttker-Schnetmann, I.; Brookhart, M. J. Am. Chem. Soc. 2004, 126,9330-8; and Göttker-Schnetmann, I.; White, P.; Brookhart, M. J. Am.Chem. Soc. 2004, 126, 1804-11; and White, P. S.; Brookhart, M.; Hill,C.; Carolina, N. Organometallics 2004, 23, 1766-1776; and Ahuja, R.;Punji, B.; Findlater, M.; Supplee, C.; Schinski, W.; Brookhart, M.;Goldman, A. S. Nat. chem. 2011, 3, 167-71; and Dobereiner, G. E.; Yuan,J.; Schrock, R. R.; Goldman, A. S.; Hackenberg, J. D. J. Am. Chem. Soc.2013, 135, 12572-5; and Shi, Y.; Suguri, T.; Dohi, C.; Yamada, H.;Kojima, S.; Yamamoto, Y. Chem. Eur. J. 2013, 19, 10672-89.) Suchphosphine, phosphinite and mixed phosphine-phosphinite based systemshave found wide spread utility as catalysts for alkane metathesis (see,Haiback, M. C. Kundu, S.; Brookhart, M.; Goldman, A. S. Acc. chem. res.2012, 45, 947-58; and Goldman, A. S.; Roy, A. H.; Huang, Z.; Ahuja, R.;Schinski, W.; Brookhart, M. Science 2006, 312, 257-61; and Ahuja, R.;Kundu, S.; Goldman, A. S.; Brookhart, M.; Vicente, B. C.; Scott, S. L.Chem. Commun. 2008, 253-5), alkyl group metathesis (see, Dobereiner, G.E., Yuan, J.; Schrock, R. R.; Goldman, A. S.; Hackenberg, J. D. J. Am.Chem. Soc. 2013, 135, 12572-5), dehydroaromatization reactions (see,Ahuja, R., Punji, B.; Findlater, M.; Supplee, C.; Schinski, W.;Brookhart, M.; Goldman, A. S. Nat. chem. 2011, 3, 167-71), alkane-alkenecoupling reactions (see, Leitch, D. C.; Lam, Y. C.; Labinger, J. A;Bercaw, J. E. J. Am. Chem. Soc. 2013, 135, 10302-5) and dehydrogenationof several other substrates. (See, Gupta, M.; Kaska, W. C.; Jensen, C.M. Chem. Commun. 1997, 461-462; and Jensen, C. M. Chem. Commun. 1999,2443-2449; and Zhang, X.; Fried, A.; Knapp, S.; Goldman, A. S. Chem.Commun. 2003, 2060-1.) Recently, there has also been an attempt tounderstand the steric effects on catalytic efficiency by systematicallyreplacing the phosphino-tert-butyl groups with phosphino methyl groups.(See, Kundu, S.; Choliy, Y.; Zhuo, G.; Ahuja, R.; Emge, T. J.; Warmuth,R.; Brookhart, M.; Krogh-Jespersen, K.; Goldman, A. S. Organometallics2009, 28, 5432-5444.)

One of the widely used hydrogen acceptors for alkane transferdehydrogenation is tert-butyl ethylene (TBE) as it is resistant toisomerization reactions. However on an industrial scale, the use of TBEis less economical. One would prefer to use hydrogen acceptors that areinexpensive and recyclable.

Despite the extensive research into new catalysts and methods forproducing valuable olefin compounds, the search for effective methods toprepare olefins from alkanes continues. Such methods would make thepreparation of valuable olefin compounds more economical and efficient.

SUMMARY

Disclosed herein is a process for dehydrogenation of an alkane to analkene. The process comprises providing an alkane feedstock comprisingat least one alkane and contacting the alkane with an iridium pincercomplex while removing hydrogen to form an alkene product. The hydrogencan be removed by a using hydrogen acceptor, flowing an inert gasthrough the reaction, refluxing the reaction in an open container, orconducting the reaction under partial vacuum.

In one embodiment the process comprises providing an alkane feedstockcomprising at least one alkane and contacting the alkane with an iridiumpincer complex in the presence of a hydrogen acceptor selected from thegroup consisting of ethylene, propene, or mixtures thereof to form analkene product.

In another embodiment, the process comprises providing an alkanefeedstock comprising at least one alkane, contacting the alkane with aniridium pincer complex to form an alkene product, and immediatelyconverting the alkene product to a secondary product.

The processes disclosed herein can accomplish facile, low-temperature(less than 300° C.) transfer dehydrogenation of alkanes (e.g., highlyabundant alkanes like pentane) with unprecedented selectivities and TONsat a reasonable rate of conversion. In certain embodiments the processesuse readily recyclable and inexpensive hydrogen acceptors. The processesdisclosed herein utilize an iridium pincer complex as a catalyst.

Further disclosed herein are specific iridium pincer complexes. Thesecomplexes have particularly efficient for dehydrogenation under theconditions disclosed herein. These iridium pincer complexes includeComplex 7: (^(iPr4)PCP)Ir(C₂H₄) and Complex 11:(p-OK-^(iPr4)PCP)Ir(C₃H₆).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram ofComplex 7: (^(iPr4)PCP)Ir(C₂H₄). Hydrogen atoms are retained only on theethylene ligand in the drawing.

FIG. 2 is a schematic diagram showing the details of the reaction ofExample 5.

FIG. 3 is a schematic diagram showing the details of the reaction ofExample 6.

FIG. 4 illustrates the synthesis procedure of Example 12.

FIG. 5 illustrates acceptorless dehydrogenation of n-dodecane asdescribed in Example 14.

DETAILED DESCRIPTION

Provided are processes for dehydrogenation of an alkane to an alkeneusing an iridium pincer complex. One advantage of the present processesis high selectivity and yield to the same carbon number product as thefeed since substantially no cracked products are formed at the lowreaction temperatures. Another advantage is the ability to produceodd-carbon number alkene products. With prior art processes, such asethylene oligomerization, only even-numbered products are obtained. Afurther advantage is relatively high selectivity to alpha olefin or1-alkene products.

In the dehydrogenation reactions, hydrogen that is co-formed during theprocess must be removed for the chemical reaction to proceed and toprevent the excess hydrogen from poisoning the catalyst. The hydrogencan be removed by a using hydrogen acceptor, flowing an inert gasthrough the reaction, refluxing the reaction in an open container, orconducting the reaction under partial vacuum.

The dehydrogenation processes of the present invention are conducted atlower reaction temperatures. At these lower temperatures, there issubstantially no cracking of the alkane feedstock. As such, theprocesses disclosed herein provide very high selectivity to an alkeneproduct with the same carbon number as the feed at reasonableconversions. The processes exhibit selectivities of greater than 80%. Incertain embodiments, the selectivities are 85% and greater. In otherembodiments, the selectivities are 90% and greater. In many embodiments,the selectivities are 95% and greater with a reasonable conversion ofabove 50%. The processes disclosed herein also provide a relatively highselectivity to alpha-olefin or 1-alkene products.

The present processes also exhibit unprecedented TONs. The presentprocesses can show a rate of 100 TON or greater at 10 minutes (based oniridium catalyst) and a turnover frequency (TOF) of 10 min⁻¹ or greater.In certain embodiments, the present processes can show a rate of 150 TONor greater at 10 minutes (based on iridium catalyst) and a turnoverfrequency (TOF) of 15 min⁻¹ or greater. In other embodiments, thepresent processes can show a rate of 200 TON or greater, or 250 TON orgreater, at 10 minutes (based on iridium catalyst) and a turnoverfrequency (TOF) of 20 min⁻¹ or greater, or 25 min⁻¹ or greater. Incertain embodiments, the present processes can show a rate of 500 TON orgreater at 10 minutes (based on iridium catalyst) and a turnoverfrequency (TOF) of 50 min⁻¹ or greater.

Embodiments in which a hydrogen acceptor is not utilized are describedherein as “non-oxidative” or “acceptor-less”. As such thesedehydrogenation reactions are conducted in the absence of a hydrogenacceptor with the hydrogen that is co-formed during the process beingremoved in an alternative way.

In the acceptor-less embodiments, the hydrogen can be removed bysparging (i.e., flowing) an inert gas through the reaction, refluxingthe reaction in an open container, and conducting the reaction underpartial vacuum.

In an embodiment where the hydrogen is removed by sparging (i.e.,flowing), an inert gas is flowed through the reaction medium. An inertgas is one that is unreactive with the iridium pincer complex underreaction conditions. Suitable inert gases include, for example, argon,helium, krypton, and the like.

In some embodiments, nitrogen may work as an inert sparging gas, if itdid not inhibit activity of the iridium pincer complex catalyst.

In other embodiments, methane can be used as an inert sparging gas.Methane is typically used as a source for fuel or H₂. When used as aninert sparging gas, any amount of H₂ that is mixed in with the methaneprovides added value and the methane with H₂ can be used without anyneed for separation. As such, any H₂ present adds value to the methanewhen used as an inert sparging gas.

In a further acceptor-less embodiment, the hydrogen can be removed byrunning the reaction under partial vacuum. The partial vacuum removesthe hydrogen and the higher boiling hydrocarbons participating in thereaction are returned to the reaction medium using a condenser.

In a further acceptor-less embodiment, the reaction is conducted underreflux in an open flask. The hydrogen is swept out of the reactionmedium as the reaction refluxes and the reaction proceeds to form alkeneproduct. This embodiment works well with higher boiling alkanes, forexample C₁₀ and C₁₂ alkanes.

In another acceptor-less embodiment, the process comprises providing analkane feedstock comprising at least one alkane, contacting the alkanewith an iridium pincer complex to form an alkene product, andimmediately converting the alkene product to a secondary product. Theconversion to a secondary product can be an oligomerization, wherein thealkene product is contacted with an oligomerization catalyst. Otherreactions to convert the alkene to a secondary product are well known tothose of skill in the art. These secondary reactions are also describedin US 2013/0090503 “Process for Alkane Oligomerization” filed 12 Sep.2013, the contents of which are hereby incorporated by reference intheir entirety.

Embodiments in which a hydrogen acceptor is utilized are describedherein as hydrogen acceptor dehydrogenation reactions. In theseembodiments the dehydrogenation reaction is conducted in a closed systemand the hydrogen produced reacts with a hydrogen acceptor molecule. Thehydrogen acceptors can be ethylene, propene, benzene, and the like, ormixtures thereof. In certain hydrogen acceptor embodiments, the hydrogenacceptors utilized are selected from the group consisting of ethylene,propene, and mixtures thereof. Ethylene, propene, and mixtures thereofare highly abundant light alkenes, readily recyclable, and inexpensive.Propene and ethylene are obtained in abundance as a by-product of oilrefining and natural gas processing.

As such, provided are processes utilizing a hydrogen acceptor selectedfrom the group consisting of ethylene, propene, and mixtures thereof.These hydrogen acceptors can be coordinated with the metal center of theiridium pincer complex. The processes using a hydrogen acceptor compriseutilizing ethylene or propene with an iridium pincer complex todehydrogenate an alkane feedstock.

The alkanes to be dehydrogenated can be C₄ to C₁₀₀ alkanes, includingfor example, pentane, octane, nonane, decane, and dodecane. In certainembodiments, the alkanes to be dehydrogenated are C₅ to C₁₀₀ alkanes.The use of iridium pincer complex catalysts disclosed herein has beenfound to give unprecedented TONs for alkane dehydrogenation both in thegas phase and in the liquid phase. The present processes can show a rateof 100 TON or greater at 10 minutes (based on iridium catalyst) and aturnover frequency (TOF) of 10 min⁻¹ or greater. The iridium pincercomplex catalysts as disclosed herein also have been found to giveunprecedented selectivity to products of the same carbon number as thefeed. These selectivities can be 90% or greater or 95% or greater atreasonable conversions of above 50%. In certain instances, the use ofiridium pincer complex catalysts also has been found to result inpreferential formation of alpha-olefins. For example, gas phasedehydrogenation can result in preferential formation of alpha-olefins.

Among other factors, it has been discovered that the transferdehydrogenation of alkanes, such as highly abundant light alkanes likebutane and pentane, can be accomplished in the gas phase using readilyrecyclable and cheap hydrogen acceptors with unprecedented turnovernumbers (TONs) and selectivities. The hydrogen acceptors are alkenessuch as propene and ethylene. It has also been discovered that, incertain instances, the transfer dehydrogenation in the gas phase canprovide preferential regioselectivity toward the alpha-olefins, e.g.,1-butene and 1-pentene. Transfer dehydrogenation of higher alkanes suchas octane, nonane, decane, and dodecane in the liquid phase with propeneor ethylene also has been found to be facile. Overall, the presentprocess provides unprecedented TONs and selectivities for alkanedehydrogenation both in the gas phase and in the liquid phase. Moreover,in certain instances, the reaction results in exceptionally slowisomerization of alpha-olefins, thereby improving desired yields ofalpha-olefins. These dehydrogenation reactions are conducted at lowertemperatures and thus result in little to no cracking of the alkanefeedstock.

The alkane conversion in the present process can be to a variety ofalkene products, but primarily to alkene products of the same carbonnumber as the alkane feedstock. A high selectivity indicates that thealkane is converted primarily to a product of the same carbon number. Assuch, there is little to no cracking. The conversion can be to an olefinor a diolefin (containing two carbon-carbon double bonds). There canalso be a small amount of conversion to a dimer, which is anoligomerization product with a carbon number greater than the alkanefeedstock.

As used herein, “selectivity” with regard to the reaction means that analkane feedstock is converted to an alkene product with the same carbonnumber. For example, at a selectivity of 90% or greater with a pentanefeedstock, 90% or greater of the pentane feedstock is converted to analkene product with five carbons (e.g., any pentene product). Theselectivity indicates that the alkane feedstock and alkene product havethe same carbon number. In certain embodiments, the dehydrogenationreaction disclosed herein provides a selectivity of 90% or greater, or95% or greater, at a reasonable conversion rate of above 50%. Thepresent processes do not yield cracking products since the processes canbe conducted at lower temperatures (<260° C.). As such, the processes'selectivities are 90% or greater, or 95% or greater, to alkenes with thesame carbon number as the starting alkane.

As used herein, the term “TON” (turnover number) refers to the alkenesproduced by a mole of iridium pincer complex before it is inactivatedor, alternatively, the hydrogen acceptor consumed by a mole of iridiumpincer complex before it is inactivated. Increased TONs are associatedwith increased conversion. For example, the present processes can show arate of 100 TON or greater at 10 minutes (based on iridium catalyst) anda turnover frequency (TOF) of 10 min⁻¹ or greater. In certainembodiments, the present processes can show a rate of 200 TON or greaterat 10 minutes (based on iridium catalyst) and a turnover frequency (TOF)of 20 min⁻¹ or greater.

The conversion can be discussed based on the mole or weight % of alkaneconverted to alkene or the mole or weight % hydrogen acceptor convertedto alkane in accepting hydrogen. The hydrogen acceptor embodiments ofthe present reaction are conducted in a closed system; therefore, theamount of alkane feedstock dehydrogenated to form alkene product issubstantially equivalent to the amount of hydrogen acceptor consumed(creating an alkane). The conversion can be in the range of from10-100%. In the present process, the conversion can be 50% or greater or75% or greater. In certain embodiments, the conversion can be 95% orgreater.

The present processes also can provide for preferential formation ofalpha-olefins or 1-alkenes. Regarding the preferential formation ofalpha-olefins, the selectivity to the alpha-olefin can be at least 20%of the converted product. In one embodiment, the selectivity to thealpha-olefin can be at least 25% of the converted product. In anotherembodiment, the selectivity to the alpha-olefin can be at least 30% ofthe converted product. In yet another embodiment, the selectivity to thealpha-olefin can be at least 50% of the converted product, and can be atleast 75% of the converted product. In one embodiment, the selectivityto the alpha-olefin is at least 80% or the converted product and can beat least 85% of the converted product.

Iridium Pincer Complex

As used herein, the term “iridium pincer complex” refers to a complexhaving a tridentate ligand that is connected to iridium via at least onemetal-carbon sigma bond with substituents ortho to this sigma bond beingheld in a fixed position and coordinating to iridium.

In certain embodiment, the iridium pincer complex can have the followingFormula I:

wherein the unspecified optionally fused ring system can be any C—Hconstruction including optional O and N heteroatoms, including non-fusedsystems and fused ring systems such as naphthalenes;“n” is an integer from 0 to 4 and each L is independently H, alkyl, oralkene;each R₁ is independently alkyl; andeach X is independently O or CH₂.

In certain embodiments, the iridium pincer complex can have thefollowing Formula (Ia):

wherein:“n” is an integer from 0 to 4 and each L is independently H, alkyl, oralkene;each R₁ is independently alkyl;each X is independently O or CH₂; andY is H or OM wherein M is alkyl, potassium (K), or solid support.

In certain embodiments, the iridium pincer complex can have thefollowing Formula (Ib):

wherein:“n” is an integer from 0 to 4 and each L is independently H or alkyl;each R₁ is independently alkyl;each X is independently O or CH₂; andY is H or OM wherein M is alkyl, K, or solid support.

In certain embodiments, the iridium pincer complex can have thefollowing Formula

wherein M is K or solid support; “n” is an integer from 0 to 4; and eachL is independently H, alkyl, or alkene.

As used herein, in connection with the above Formulae, the term “alkyl”means a branched or straight chain, saturated hydrocarbon radical having1 to 10 carbons. Exemplary alkyl groups include methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, and the like. Incertain embodiments, the alkyl has 1 to 5 carbons. In other embodiments,the alkyl has 1 to 4 carbons.

As used herein, in connection with the above Formulae for the iridiumpincer complex, the term “alkene” means a branched or straight chain,unsaturated hydrocarbon having 2 to 5 carbons and one carbon-carbondouble bond. Exemplary alkene groups include ethylene, propene,but-1-ene, but-2-ene, and 2-methylpropene. In certain embodiments, thealkene has 2 or 3 carbons. In these embodiments, the alkene is ethyleneor propene.

The iridium pincer complex can be as described in U.S. Pat. No.6,982,305 to Nagy, which is incorporated herein by reference in itsentirety.

In certain embodiments the iridium pincer complex can also be selectedfrom the group consisting of:

and mixtures thereof.

Certain of the complexes identified herein are novel iridium pincercomplexes. For example, Complex 7: (^(iPr4)PCP)Ir(C₂H₄) and Complex 11:(p-OK-^(iPr4)PCP)Ir(C₃H₆) are particularly useful. Complexes 7 and 11can be unsupported or immobilized on a solid support. In an unsupportedembodiment, the complexes can be coated on the glass container in whichthe dehydrogenation reaction occurs.

The iridium pincer complexes can be a pure solid catalyst compound. Theiridium pincer complex can be unsupported or, alternatively, immobilizedon a solid support. When supported on solid support, the iridium pincercomplex is anchored via a polar anchoring group. The iridium pincercomplexes can be supported on any suitable support, such as solidoxides, including but not limited to alumina, silica, titania, magnesia,zirconia, chromia, thoria, boria, beryllia, and mixtures thereof. Incertain embodiments, the solid support can be, for example, silica,γ-alumina, basic alumina, florisil, or neutral alumina. In anembodiment, the solid support is florisil or neutral alumina.

In one embodiment of the present processes, the iridium pincer complexutilized is Complex 7: (^(iPr4)PCP)Ir(C₂H₄) or Complex 11:(p-OK-^(iPr4)PCP)Ir(C₃H₆). Complex 7 or Complex 11 can be unsupported orimmobilized on a solid support. In a particular embodiment, the iridiumpincer complex is Complex 11: (p-OK-^(iPr4)PCP)Ir(C₃H₆) immobilized on asolid support. The solid support can be florisil or neutral alumina. Inanother embodiment, the iridium pincer complex is Complex 7:(^(iPr4)PCP)Ir(C₂H₄) immobilized on a solid support. The solid supportcan be florisil or neutral alumina.

When the iridium pincer complex is immobilized on a solid support, itcan exhibit unexpected advantages in the dehydrogenation processdisclosed herein. In one embodiment, the iridium pincer compleximmobilized on a solid support can dehydrogenate an alkane in thepresence of a hydrogen acceptor such as ethylene or propene withunprecedented selectivities, rates, and TONs. The supported iridiumpincer complex can also exhibit better activity and recyclability in thedehydrogenation process disclosed herein than an unsupported complex.

It has been discovered that the iridium pincer complex immobilized on asolid support can catalyze dehydrogenation at lower temperatures (160°C.-260° C.) with unprecedented TONs and selectivities.

Alkane Feedstock

The alkane feedstock comprises at least one alkane. As used herein, theterm “alkane” refers to a branched or straight chain, saturatedhydrocarbon having 4 to 100 carbons. Exemplary alkanes include n-butane,isobutane, n-pentane, isopentane, and neopentane. In certainembodiments, the alkane has 5 to 100 carbons. The alkane can be, forexample, a butane (e.g. all isomers of butane, including, for example,n-butane, 2-methylpropane, and the like), a pentane (e.g. all isomers ofpentane, including, for example, n-pentane, 2-methylbutane, and thelike), an octane (e.g. all isomers of octane, including, for example,n-octane, 2,3-dimethylhexane, 4-methylheptane, and the like), or adodecane (e.g. all isomers of dodecane, including, for example,n-dodecane, 2-methyl-3-methyldecane, 3-ethyldecane, and the like). In anembodiment, the alkane comprises a butane. In another embodiment, thealkane comprises a pentane. In yet another embodiment, the alkanecomprises an octane. In another embodiment, the alkane comprises adodecane. In an embodiment, the alkane is selected from the groupconsisting of a butane, a pentane, an octane, a nonane, a decane, adodecane, and mixtures thereof. In certain embodiments, the alkane is astraight chain alkane.

The alkane feedstock can comprise a single alkane or a mixture ofalkanes. As such, the alkane to be dehydrogenated can be a single alkaneor a mixture of alkanes. The alkane can be a mixture of isomers of analkane of a single carbon number. The alkane feedstock can comprisehydrocarbons in addition to the alkane or mixture of alkanes to bedehydrogenated. A hydrocarbon feed composition from any suitable sourcecan be used as the alkane feedstock. Alternatively, the alkane feedstockcan be isolated from a hydrocarbon feed composition in accordance withknown techniques such as fractional distillation, cracking, reforming,dehydrogenation, etc. (including combinations thereof). For example,n-paraffin as a feed can be obtained by either by adsorption orextractive crystallization. One suitable source of the alkane feedstockdescribed further herein, by no means to be taken as limiting, is theoutput of a Fischer-Tropsch reaction system.

The production of hydrocarbon compositions comprising alkanes fromsynthesis gas by Fischer-Tropsch catalysis is well known and can becarried out in accordance with known techniques by reaction of asynthesis gas in the presence of Fischer-Tropsch catalyst in a reactor.Any suitable catalyst can be used, including but not limited to iron andcobalt catalysts. See, e.g., U.S. Pat. No. 6,217,830 to Roberts andKilpatrick; see also U.S. Pat. Nos. 6,880,635; 6,838,487; 6,201,030;6,068,760; 5,821,270; 5,817,701; 5,811,363; 5,620,676; and 2,620,347.

The production of synthesis gas from carbonaceous or organic materials,such as coal (including coal fines), natural gas, methane, refinerybottoms, vegetative materials such as wood or other biomass, andcombinations thereof, is well known and can be carried out in accordancewith known techniques. In some embodiments such production involves thepartial oxidation of the carbonaceous or organic material at elevatedtemperatures, and optionally elevated pressures, with a limited volumeof oxygen. The reaction is preferably carried out in a reactor intowhich the material is fed, together with additional agents such assteam, carbon dioxide, or various other materials. See e.g., U.S. Pat.No. 4,959,080; see also U.S. Pat. No. 4,805,561.

Alkene Product

The alkene product comprises at least one alkene. As used herein, inconnection with the alkene product, the term “alkene” refers to abranched or straight chain, unsaturated hydrocarbon having 4 to 100carbons and one or more carbon-carbon double bonds. In certainembodiments the alkene product comprises 5 to 100 carbons. In certainembodiments the alkene product comprises 4 to 100 carbons and one or twodouble bonds. In other embodiments, the alkene has 5 to 100 carbons andone or two double bonds. In yet other embodiments, the alkene has 4 to100 carbons and one double bond. In certain other embodiments, thealkene has 5 to 100 carbons and one double bond. The alkene can be, forexample, a butene (e.g., all isomers of butene, including, for example,1-butene, 2-butene, 2-methyl-1-propene, and the like), a pentene (e.g.,all isomers of pentene, including, for example, 1-pentene, 2-pentene,and the like), an octene (e.g., all isomers of octene, including, forexample, 1-octene, 2-octene, 2-methyl-3-heptene, and the like), or adodecene (e.g., all isomers of dodecene, including, for example,1-dodecene, 2-dodecene, 2-methyl-3-undecene, and the like). In anembodiment, the alkene comprises a butene. In another embodiment, thealkene comprises a pentene. In yet another embodiment, the alkenecomprises an octane. In another embodiment, the alkene comprises adodecene. In an embodiment, the alkene is selected from the groupconsisting of a butene, a pentene, an octene, a nonane, a decane, adodecene, and mixtures thereof.

One advantage of the present processes is high selectivity and yield tothe same carbon number product as the feed since no cracked products areformed at the low reaction temperatures. Another advantage is theability to produce odd-carbon number alkene products. In the presentprocesses, the alkane feedstock is converted to an alkene product withthe same carbon number. For example, at a selectivity of 90% or greaterwith a pentane feedstock, 90% or greater of the pentane feedstock isconverted to an alkene product with five carbons (e.g., any penteneproduct). In certain embodiments, the dehydrogenation reaction disclosedherein provides a selectivity of 90% or greater, or 95% or greater, at areasonable conversion rate of above 50%.

Primarily, the alkene is the same carbon number as the feed. The alkenecan comprise a single alkene or a mixture of alkenes. The alkene can bea mixture of isomers of an alkene of a single carbon number. The alkenecan have a double bond at the primary position (e.g., 1-butene,1-pentene, 1-octene, 1-dodecene) such that the alkene is analpha-olefin.

The alkene product can contain an alkene with one double bond, a diene(i.e., an alkene with two carbon-carbon double bonds), a dimer, andmixtures thereof.

Reaction Conditions

In general, the dehydrogenation reaction can be run under conventionaldehydrogenation reaction conditions. However, the iridium pincercomplexes disclosed herein do not require high temperatures orpressures. Therefore, the reaction can be run at a reaction temperatureless than 300° C. Higher temperatures up to 400° C. or 500° C. or highercan be used, but are not necessary and are not desired. Suitabletemperatures include, for example, a temperature in the range of 160°C.-260° C. In certain embodiments a temperature in the range of 200°C.-260° C. can be utilized. In other embodiments, a temperature in therange of 225° C.-250° C. can be utilized. In yet other embodiments atemperature in the range of 240° C.-250° C. can be utilized. In anembodiment, a temperature of about 240° C. is used, which temperature issufficient to maintain ethylene or propylene in the gaseous phase. Inanother embodiment, a temperature of about 200° C. is used. In yetanother embodiment, a temperature of about 160° C. is used. The pressureis adjusted accordingly.

Conducting the dehydrogenation reaction at temperatures of less than300° C. (e.g., 160° C.-260° C.) results in extremely little to nocracking of the alkane feedstock. Accordingly, the presentdehydrogenation reactions can be run with unprecedented selectivities.

The length of reaction time with best results for selectivity variesbased upon the catalyst. The reaction time is generally in the range offrom about 1 minute or less (e.g., about 30 seconds) up to 24 hours. Thereaction time can be up to about 10 minutes, up to about 40 minutes, upto about 80 minutes, up to about 100 minutes, up to about 180 minutes,or up to about 600 minutes. The reaction time can be about 10 minutes,about 40 minutes, about 80 minutes, about 100 minutes, about 180minutes, or about 600 minutes. In one embodiment, the reaction time isfrom about 10-100 minutes. Alternatively, the reaction time can be fromabout 10-180 minutes. In another embodiment, the reaction time can befrom about 20-180 minutes. In another embodiment, the reaction time canbe from about 40-100 minutes. In yet another embodiment, the reactiontime can be from about 40-180 minutes. The reaction time can be fromabout 10-40 minutes, about 10-80 minutes, about 10-100 minutes, about10-180 minutes, or about 10-600 minutes.

In an embodiment, the reaction takes place in the presence of a solidcatalyst and a gaseous hydrogen acceptor and a gaseous or liquid alkane.The use of a solid catalyst also works well with a gaseous phase for thealkane and for the hydrogen acceptor. A liquid phase can also be usedfor the reaction. While a gas phase system or liquid phase system can beused, as discussed, a three phase system of solid-liquid-gas can also besuccessful. In a three phase system, the catalyst can be a solid; thehydrogen acceptor can be gaseous; and the alkane can be liquid.

As used herein, the term “gas phase” refers to the alkane and thehydrogen acceptor both being gaseous during the dehydrogenationreaction. However, during the “gas phase” reaction, the catalyst can besolid, liquid, or gas. In an embodiment, the reaction is conducted undersupercritical conditions.

As used herein, the term “liquid phase” refers to the alkane and thehydrogen acceptor both being liquid during the dehydrogenation reaction.However, during the “liquid phase” reaction the catalyst can be solid,liquid, or gas.

The reaction can be run with varied catalyst configurations. Forexample, the reaction is run in a stirred reactor in one embodiment. Thereaction can also be run in a fixed bed or fluidized bed reactor. Thereactor can be a packed-bed reactor, trickle-bed reactor, bubble-columnreactor, ebullating-bed reactor, and the like. The system to be run,whether gas, liquid, or three phase, helps to determine the catalystconfiguration and type of reactor to be used. The reaction choice isbased on a fundamental characterization of the reaction.

For example, when using sparging to remove hydrogen, a continuousstirred tank reactor can be used. Bubble column reactors can also beutilized to conduct gas-liquid reactions. A fixed bed reactor with asupported iridium pincer complex can be utilized with counter-currentflow of a stripping gas (e.g., Ar).

The following examples are provided to better illustrate the processdisclosed herein. The examples are meant to be solely illustrative, andnot limiting.

Examples

As demonstrated in Examples 1 and 2 below, it has been found thatiridium pincer complex catalyzed dehydrogenation of pentane with propeneor ethylene at temperatures below 300° C., for example 240° C., resultsin reactions occurring in the gas phase. In Examples 1 and 2, pentanecontaining catalytic amounts of iridium pincer complex catalysts wassubjected to low temperatures under propene or ethylene atmosphere insealed vials with large head space. In many cases, such conditionsresulted in the iridium pincer complex catalysts splashing off to coatthe glass surface leading to very high activity and nearly fullconsumption of the gaseous acceptors.

In the gas phase transfer dehydrogenation of pentane with propene as thehydrogen acceptor of Example 1, while Complex 7: (^(iPr4)PCP)Ir(C₂H₄)gave very good rates and conversion, the conversion was also high withComplex 3: (^(tBu2Me2)PCP)IrH₄. On the other hand, in an analogous gasphase reaction with ethylene as the hydrogen acceptor of Example 2,Complex 7: (^(iPr4)PCP)Ir(C₂H₄) not only showed a high rate but alsoresulted in excellent conversion. Further, with ethylene as acceptor,Complex 7: (^(iPr4)PCP)Ir(C₂H₄) showed exceptional preference towardformation of 1-pentene. Interestingly, this selectivity observed in thegas phase does not substantially decrease and remains almost the same atlonger reaction times.

Example 1: Dehydrogenation of n-Pentane with Propene

In a typical experimental set up, a 100 μl stock solution of n-pentanecontaining 1 mM iridium pincer complex catalyst was taken in a fewcustom made thick walled 1.5 ml vials inside a glove box. The vials werethen connected to Kontes adapter via tygon tubings and degassed in ahigh vacuum line. One atmosphere of propene was then introduced to thesystem and the kontes valves were sealed. The contents of the vials werefrozen in liquid nitrogen and the vials were flame sealed. Note that oneatm propene charged in a 3 ml space condenses to a 1.5 ml vial spaceupon flame sealing rendering the amount of propene in each vial to beabout 2 atm. The vials were then placed in a pre heated aluminum blockinside a gas chromatography (GC) oven maintained at 240° C. andsubjected to interval free heating for a stipulated time. The GC ovenwas then cooled to room temperature, the vials were taken out, thecontents were frozen in liquid nitrogen and the tubes were broken open.The contents of each vial were analyzed by GC.

The vapor pressure of n-pentane at 240° C. is calculated to be 52 atm. Apentane stock solution (100 μl) in each of these 1.5 ml vials cangenerate about 24 atm if all of the pentane goes to the gas phase at240° C. The transfer dehydrogenation of n-pentane with propene in thesevials is essentially in the gas phase.

TABLE 1 Dehydrogenation of n-pentane catalyzed by pincer iridiumcomplexes at propene pressure of 2 atm (“1.2M”) at 240° C. Trans-2-Cis-2- 1,3- Total propene 1-pentene Catalyst Time 1-Pentene PentenePentene pentadienes Olefins consumed Selectivity Entry 1 mM (min) mM mMmM mM mM mM {%} % 1^(a) Complex 1 10 15 3 2 — 20 20 {2%} 75 40 17 2 1 —20 20 {2%} 85 180 ND ND ND ND ND ND ND 2^(b) Complex 5 10 18 3 1 1 23 24{2%} 75 40 ND ND ND ND ND ND ND 180 20 3 1 1 25 26 {2%} 77 3^(b) Complex2 10 0 0 0 0 0 0 40 50 9 0 0 59 59 {5%} 85 180 36 8 1 0 45 45 {4%} 804^(a) Complex 3 10 113 140 63 25 341 366 {30%} 33 40 152 210 95 43 500543 {44%} 30 180 195 ± 14 409 ± 25  194 ± 16 148 ± 14 945 ± 65 1093{95%} 21 5^(a) Complex 7 10 143 ± 7  312 ± 9  140 ± 5 40 ± 1 634 ± 22674 {55%} 21 40 170 ± 6  422 ± 4  188 ± 2 70 ± 0 850 ± 1  920 {75%} 18180 226 ± 14 493 ± 11 226 ± 9 108 ± 7  1054 ± 13  1162 {95%} 19 6^(b)Complex 6 10 116 ± 11 34 ± 6  16 ± 2 3 169 ± 19 172 ± 19 {13%} 67 40 20781 39 9 336 345 {28%} 60 180 183 80 38 10 311 321 {26%} 57 7^(a) Complex8 10 69 ± 9 50 ± 1 19 3 141 ± 11 144 ± 11 {11%} 48 40 119 145 50 14 328342 {28%} 36 180 168 250 82 21 521 543 {44%} 32 8^(a) Complex 9 10 79 274 2 112 114 {9%} 69 40 90 33 6 2 131 133 {11%} 68 180 100 49 8 4 161 165{13%} 61 9^(b) Complex 4 10 0 0 0 0 0 0  0 40 0 0 0 0 0 0  0 180 4 3 1 —8 8 {1%} 50 Reaction conditions; 1 mM pincer iridium catalysts in neatpentane [8.7M] under 2 atm propene “[1.2M]”at 240° C., ^(a)Thesecatalysts are found to coat the glass surface, ^(b)These catalysts forminsoluble residues at the bottom of the vial after the reaction

The transfer dehydrogenation of n-pentane was first tested with Complex1: (^(tBu4)PCP)IrH₄ and its p-methoxy derivative parent iridium pincercomplex Complex 5: (p-OMe^(tBu4)PCP)IrH₄. These catalysts showed goodselectivity toward 1-pentene but quite surprisingly, the selectivityremained almost the same at longer reaction times (Entries 1 and 2,Table 1). The runs were repeated for additional iridium pincercomplexes, under the same conditions, with the results shown in Table 1.

Complex 2: (^(tBu3Me)PCP)IrH₄ where one of the t-Bu groups issubstituted with a Me group showed a negligible improvement in catalyticactivity (Entry 3, Table 1). However, high selectivity toward 1-pentenewas uniformly observed at all times. Substitution of the second t-Bugroup by a Me group as in Complex 3: (^(tBu2Me2)PCP)IrH₄ showed adrastic increase in the rate and conversion of the reaction. After 180minutes the amount of pentenes formed corresponded to consumption ofalmost 95% of the propene. These reactions were less selective toward1-pentene showing a selectivity of only 33% and 21% after 10 and 180minutes respectively.

In general, for the iridium pincer complex catalyzed transferdehydrogenation of pentane with propene, it was believed that thecatalyst would be present as a solid mass at the bottom of the vesselwhen all substrates are in the gas phase at 240° C. As such, it wasgenerally believed that one would encounter substrate mixing problemsand hence low conversions. Hence, the high conversions obtained in thepropene reactions with Complex 3: (^(tBu2Me2)PCP)IrH₄ as the catalystwere quite surprising and rationally challenging. At this stage, it wasobserved that in the reactions with Complex 2: (^(tBu3Me)PCP)IrH₄ vialsobtained after heating at 240° C. at various times contained insolubleresidues at the bottom and a clear colorless pentane/pentene mixture(Entry 3, Table 1). On the other hand, in the case of reactions withComplex 3: (^(tBu2Me2)PCP)IrH₄ the vials obtained after heating at 240°C. at all times had a clear orange colored solution. In one of runs forthe reaction with Complex 3: (^(tBu2Me2)PCP)IrH₄ the GC oven was cooledto 60° C. from 240° C. and slowly opened taking all the safetyprecautions. At this stage the top portion of the vial was cool and thebase was still hot as it was placed inside the aluminum block. A videoof the vial recorded at this juncture clearly showed bright red dropletsformed at various positions at the topmost portions of the vial. As thevial cooled, the red droplets condensed into the solution. Oneexplanation is that at temperatures as high as 240° C., the catalysteither vaporizes and migrates to the top of the vial or is splashed offto the sides by the sudden vaporization of the liquid essentiallycoating the glass during the process. As the vial cools, the pentanewashes the catalyst from the glass resulting in bright red dropletswhich condense as an orange colored solution.

Independent tests were performed under identical conditions but in theabsence of pentane to investigate the possibility of vaporization ofpincer catalysts. These tests indicated that the iridium pincer complexcatalysts neither migrated to the top nor coated the glass surface whenheated at 240° C. under propene atmosphere. Hence, it is likely thatwhen a pentane solution containing iridium pincer complex catalyst isheated at 240° C., the catalysts are splashed off to the sides of thevessel and depending on the morphology of the catalyst, it eitherprefers to stick to the glass surface or fall off. In many instances,the catalysts which were observed to coat the glass showed goodactivity.

When Complex 7: (^(iPr4)PCP)Ir(C₂H₄) was used for the transferdehydrogenation of pentane under 2 atm of propene, the catalyst wasfound to coat the glass. The dehydrogenation catalyzed by Complex 7:(^(iPr4)PCP)Ir(C₂H₄) proceeded at twice the rate observed with Complex 3but with comparable conversion (Entry 5, Table 1) albeit with lowselectivity. However, its p-methoxy-derivative Complex 6:(p-OMe^(iPr4)PCP)Ir(C₂H₄) showed a slower rate and low conversion (Entry6, Table 1). The reaction also exhibited high selectivity toward1-pentene at all times and the reaction leveled off after 40 minutes.This catalyst does not coat the glass and the catalyst forms insolubleresidue upon heating under propene atmosphere.

Complex 8: (^(iPr4)PCOP)Ir(C₂H₄) showed a similar behavior as Complex 3:(^(tBu2Me2)PCP)IrH₄ and Complex 7: (^(iPr4)PCP)Ir(C₂H₄) by coating theglass. The activity of this catalyst was good (Entry 7, Table 1) butless than that of either Complex 3 or Complex 7, though the selectivitytoward 1-pentene was slightly higher compared to Complex 3 or Complex 7.Though Complex 9: (^(iPr4)Anthraphos)Ir(C₂H₄) was observed to coat theglass, its activity was surprisingly not as good as expected (Entry 8,Table 1).

In an attempt to increase the amount of dehydrogenated products, thereaction was performed under 4 atm propene [“2.5 M”] using Complex 7:(^(iPr4)PCP)Ir(C₂H₄) as the catalyst at 240° C. The reaction showed ahigh rate of 1350 turnovers after 10 minutes with 30% selectivity toward1-pentene. No appreciable improvement in conversion at longer times wasobserved.

It was discovered with regard to this pentane and propene chemistry thatthe use of cheap hydrogen acceptors for light alkane dehydrogenation wasquite viable. In contrast to normal expectations, almost uniformselectivity at all times is observed. In the propene reactions, catalystthat gave excellent selectivity toward alpha-olefins resulted in lowconversions and those that gave rise to high TONs were less selective.

Example 2: Dehydrogenation of n-Pentane with Ethylene

The transfer dehydrogenation of pentane with ethylene as acceptor wasattempted using a few selected catalysts (Complexes 3, 6, 7, 8 and 9)that demonstrated acceptable activity in the propene reactions. Thetransfer dehydrogenation of pentane with ethylene catalyzed by Complex3: (^(tBu2Me2)PCP)Ir(H₄) proceeded at a rate of about 100 turnovers in10 minutes with a selectivity of about 70% toward 1-pentene (Entry1,Table 2). After 180 minutes the conversion was about 261 turnovers andthe selectivity had dropped to 50%. The selectivity at initial times isalmost the same but as the reaction goes from 40 minutes to 180 minutes,the drop in selectivity is about 20% (Entry 1, Table 2). This drop inselectivity is more pronounced than in the propene reactions catalyzedby Complex 3: (^(tBu2Me2)PCP)IrH₄ (10% drop, Entry 4, Table 1). Uponcomparing the pentane dehydrogenation with either propene or ethylenecatalyzed by Complex 3: (^(tBu2Me2)PCP)IrH₄, it is apparent that theselectivity toward 1-pentene is slightly higher with ethylene as theacceptor. The best comparison would be the 10 minutes run (360 TON, 30%selectivity) for propene reactions in Table 1 (Entry 4) and the 180minutes run (260 TON, 50% selectivity) for ethylene reactions in Table 2(Entry 1).

Analogous reaction catalyzed by Complex 7: (^(iPr4)PCP)Ir(C₂H₄) showedrates comparable to Complex 3: (^(tBu2Me2)PCP)IrH₄ but with excellentselectivity. Comparison of the regioselectivities of Complex 7 andComplex 3 under identical TONs (10 and 180 minutes of Entry 1 with 10and 40 minutes of Entry 2) was indicative of the excellentregioselectivity of Complex 7: (^(iPr4)PCP)Ir(C₂H₄) compared to Complex3: (^(tBu2Me2)PCP)IrH₄. Further, Complex 7: (^(iPr4)PCP)Ir(C₂H₄)exhibited very high conversion compared to Complex 3 or any othercatalysts screened in Table 2. It is also noteworthy that Complex 7:(^(iPr4)PCP)Ir(C₂H₄) catalyzed pentane dehydrogenation with ethyleneexhibited higher regioselectivity than the analogous reaction withpropene as acceptor under comparable TONs. While 21% selectivity toward1-pentene is observed after 10 minutes with propene as acceptor (670TON, Entry 5, Table 1), use of ethylene gives a regioselectivity of 65%after 100 minutes (680 TON, Entry 2, Table 2).

The rest of catalysts Complex 6: (p-OMe^(iPr4)PCP)Ir(C₂H₄), Complex 8:(^(iPr4)PCOP)Ir(C₂H₄) and Complex 9: (^(iPr4)Anthraphos)Ir(C₂H₄) thatwere screened for pentane dehydrogenation with ethylene as acceptors(Entries 3, 4 and 5) though exhibited selectivities higher than thecorresponding reactions with propene as acceptors in Table 1, thecatalytic activity was not appreciable. Note that all reactions studiedin Tables 1 and 2 resulted in catalyst splashing off and coating theglass. These studies indicate that though coating the glass is essentialto counter the substrate mixing problem, the activity depends on thenature of the catalyst. For instance, Complex 3: (^(tBu2Me2)PCP)IrH₄coated the glass in pentane dehydrogenation reactions with both propeneand ethylene as acceptor; however, the catalytic activity wasexceptional only in the case of propene as acceptor. With ethylene asacceptor though Complex 3: (^(tBu2Me2)PCP)IrH₄ exhibited a high rate,the conversion after 180 minutes was low. The results are shown in Table2.

TABLE 2 Dehydrogenation of n-pentane catalyzed by pincer iridiumcomplexes at ethylene pressure of 2 atm (“1.2M”) at 240° C. Trans-2-Cis-2- 1,3- Total Ethylene 1-pentene Catalyst Time 1-Pentene PentenePentene pentadienes Olefins Consumed Selectivity Entry 1 mM (min) mM mMmM mM mM mM {%} % 1 Complex 3 10 70 ± 3 18 ± 2 8 ± 1 1 ± 0 98 ± 6 98{8%} 71 40 90 29 12 2 133 135 {11%} 70 180 135 79 33 7 254 261 {21%} 522 Complex 7 10 60 ± 0  7 ± 2 3 ± 1 2 ± 1 72 ± 5 75 {6%} 83 40 251 44 225 322 327 {27%} 78 100 427 135 70 28  660 688 {56%} 65 180 419 176 8841  724 765 {62%} 58 3 Complex 6 10 36 3 2 — 41 41 {3%} 88 40 66 10 4 —80 80 {6%} 83 180 120 23 11 2 156 158 {13%} 77 4 Complex 8 10 12 3 2 —17 17 {1%} 71 40 34 7 4 — 45 45 {4%} 76 180 ND ND ND ND ND ND ND 5Complex 9 10 36 4 1 — 41 41 {3%} 88 40 46 5 2 — 53 53 {4%} 87 180 118 285 1 152 153 {12%} 77 Reaction conditions; 1 mM pincer iridium catalystsin neat pentane [8.7M] under 2 atm ethylene “[1.2M]” at 240° C.

Example 3: Dehydrogenation of n-Octane with Propene

As demonstrated in Examples 3 and 4, transfer dehydrogenation of higheralkanes such as octane and dodecane in the liquid phase with eitherpropene or ethylene has been found to be facile. In Example 3, Complex7: (^(iPr4)PCP)Ir(C₂H₄) was found to be the most efficient catalyst withboth propene and ethylene as acceptors.

Example 3 can be viewed as demonstrating exceptional selectivity ofiridium pincer complex catalyzed transfer dehydrogenation reactionstoward alpha-olefins when the reaction is performed in the liquid phase.This example can also be viewed as demonstrating high turnover numbersfor iridium complex catalyzed transfer dehydrogenation performed in theliquid phase. This example can further be viewed as demonstrating octanetransfer dehydrogenation rapidly occurs using ethylene or propene as ahydrogen acceptor where the reaction is essentially in the liquid phase.Octane was used in the same glass vials under similar ethylene orpropene pressures as discussed for the pentane reactions.

The vapor pressure of n-octane at 240° C. is calculated to be 11 atm. Aoctane stock solution (100 μl) in each of these 1.5 ml vials producesabout 17 atm if all of the octane would vaporize. Therefore, thetransfer dehydrogenation of octane with propene in these vials isessentially in the liquid phase.

The transfer dehydrogenation of octane was first tested at 240° C. with1 mM Complex 7: (^(iPr4)PCP)Ir(C₂H₄) at a propene pressure of 2 atm.With 2 atm propene in a 1.5 ml vial, one has a concentration of about“1.2 M” propene if all of the hydrogen acceptor were to be in solution.Complex 7: (^(iPr4)PCP)Ir(C₂H₄) was highly active for this reactiongiving 449 TON after 10 minutes and reaching 1156 TON after 180 minutesindicating that most of the propene has been consumed at this stage(Entry 1, Table 3). The reaction occurring in the liquid phase permittedincrease of propene pressures to probe for higher TONs. Increasingpropene pressure had a favorable effect on the rates and conversion. Ata propene pressure of 6.5 atm, a rate as high as 1756 TON was obtainedwith a conversion of 2651 TON (2651 TON of total olefins using 1 mM(^(iPr4)PCP)Ir(C₂H₄) as catalyst). Runs were made using variouscatalysts and various propene pressures. The runs and their results aredetailed in Table 3.

TABLE 3 Dehydrogenation of n-octane catalyzed by pincer iridiumcomplexes under various propene pressures at 240° C. Higher Totalpropene 1-octene Catalyst Propene Time Monoenes mM Dienes fractionsOlefins consumed Selectivity Entry 1 mM P “M” min 1-octene Total mM mMmM mM {%} % 1  Complex 7   2 atm 10 160 405 38 6 449 400 {41%} 36 “1.2M”40 175 724 124 18 866 1026 {84%} 20 180 210 ± 86  983 ± 150 166 ± 29 36± 2 1156 ± 119 1364 {111%} 18 2^(a) Complex 7 3.5 atm 10 155 897 183 501130 1413 {66%} 14 “2.1M” 40 190 1080  222 63 1365 1713 {78%} 14 180 1641190  273 100 1563 2036 {95%} 10 3^(a) Complex 7 6.5 atm 10 242 ± 201393 ± 45 232 ± 93 131 ± 34 1756 ± 172 2250 {56%} 14 “4.0M” 40 198 1577 468 351 2396 3566 {89%} 8 180 219 1706  535 410 2651 4006 {100%} 8  4^(b) Complex 3 6.5 atm 10 68 ± 4  204 ± 20  2 ± 1 1 206 ± 32 278 {7%} 33“4.0M” 40 143 972 140 60 1172 1432 {36%} 12 180 148 959 126 39 1124 1328{33%} 13 5^(a) Complex 6 6.5 atm 10 198 671 31 6 708 751 {19%} 28 “4.0M”40 259 1022  89 33 1144 1299 {32%} 22 180 253 940 70 18 1028 1134 {28%}25 6^(a) Complex 8 6.5 atm 10  81 296 12 1 309 323 {8%} 26 “4.0M” 40 137558 39 7 604 657 {16%} 23 180 151 560 48 3 611 665 {17%} 24  7 ^(b)Complex 9 6.5 atm 10 248 1132  97 25 1254 1401 {35%} 20 “4.0M” 40 276 ±4  1268 ± 82 109 ± 23  21 ± 12 1398 1549 {39%} 20 180 277 1091  82 211194 1318 {33%} 23 Reaction conditions; 1 mM pincer iridium catalysts inneat pentane [8.7M] under 2 atm propene “[1.2M]”, ^(a)These catalystform insoluble residues at the bottom of the vial after the reaction,^(b) These catalysts are found to vaporize and coat the glass surface

The dehydrogenation of n-octane over selected iridium pincer complexesunder ethylene pressure of 6.5 atm at 240° C. was demonstrated. Resultsand details of the runs are shown in Table 4.

TABLE 4 Dehydrogenation of n-octane catalyzed by pincer iridiumcomplexes at ethylene pressure of 6.5 atm (“4.0M”) at 240° C. HigherTotal propene 1-octene Catalyst Time Monoenes mM Dienes fractionsOlefins consumed Selectivity Entry 1 mM min 1-octene Total mM mM mM mM{%} % 1^(a) Complex 7 10 200 506 17 4 527 552 {14%} 38 40 ND ND ND ND NDND ND 180 377 1224 64 17  1305 1403 {35%} 29 2^(b) Complex 9 10 172 3192 — 321 323 {8%} 54 40 229 492 5 1 498 505 {13%} 46 180 251 771 22 1 794818 {20%} 32 3^(a) Complex 3 10 103 388 16 2 406 424 {11%} 25 40 126 51728 6 551 585 {15%} 23 180 127 505 28 6 539 573 {14%} 24 4^(a) Complex 610  25  36 1 — 37 38 {1%} 68 40 114 178 1 — 179 180 {4%} 64 180 ND ND NDND ND ND ND 5^(b) Complex 8 10  47  92 1 — 93 94 {2%} 50 40  49  88 1 —89 90 {2%} 55 180 ND ND ND ND ND ND ND Reaction conditions; 1 mM pinceriridium catalysts in neat pentane [8.7M] under 6.5 atm ethylene “[6.5M]”

Example 4: Dehydrogenation of n-Dodecane with Ethylene

N-dodecane was dehydrogenated using ethylene as the hydrogen acceptor.The details of the reaction and the results of the runs are set forth inTable 5. This example can be viewed as demonstrating high turnovernumbers for iridium complex catalyzed transfer dehydrogenation performedin the liquid phase. This example can also be viewed as demonstratingdodecane transfer dehydrogenation rapidly occurs using ethylene as ahydrogen acceptor where the reaction is essentially in the liquid phase.

TABLE 5 (^(iPr4)PCP)Ir(C₂H₄) catalyzed dehydrogenation of η-dodecane[4.4M] under 4 atm of ethylene [2.4M] at 240° C. Total Ethane mM{%} =Monoenes Alignment Acceptor Time Olefins Total Double 1-Dodecene [mM]Catalyst of the vial P [M] Min mM bonds^(a) {Selectivity %}^(b) TotalComplex 7

Ethylene 10 440 ± 5 450

18%

182 ± 2

42%

428 ± 6 4 atm 40  768 ± 11 815

33%

222 ± 2

30%

 726 ± 13 2.4M 180 1290 ± 2  1926

80%

285 ± 5

30%

830 ± 3 ^(a)Ethane formed = Total dehydrogenation = Total double bondsformed, ^(b)Selectivity = (1-decene/Total monoenes) × 100

indicates data missing or illegible when filed

Example 5: Dehydrogenation of n-Butane with Propene

As demonstrated in Example 5, it has been found that iridium pincercomplex catalyzed dehydrogenation of butane with propene at temperaturesbelow 300° C., for example at 240° C., results in reactions occurring inthe gas phase.

The transfer dehydrogenation of n-butane with propene in the gas phasewas tested with Complex 10: (^(iPr4)PCP)Ir. The details of the reactionand the results of the runs are set forth in Table 6 and FIG. 2. Highselectivity for 1-butene and significant amounts of butadienes wereobserved.

TABLE 6 Dehydrogenation of 3 atm of n-butane [6.1M] catalyzed by pinceriridium complex at propene pressure of 3 atm (“6.1M”) at 240° C. Total1-Butene Catalyst Olefin Butadiene 1-Butene Fraction Entry 1 mM Time TONTON TON (%) 1 Complex 10 10 335 40 185 65 40 590 40 370 65 180 680 65280 45

Example 6: Dehydrogenation of n-Pentane with Propene Using SupportedCatalyst

As demonstrated in Example 6, it has been found that supported iridiumpincer complex catalyzed dehydrogenation of pentane with propene attemperatures as low as 200° C. results in reactions occurring in the gasphase with unprecedented rates and TONs. Example 6 also demonstratessupported iridium pincer complexes catalyze dehydrogenation of pentanewith propene at temperatures as low as 200° C. with better activity andrecyclability than unsupported iridium pincer complex catalysts.

The transfer dehydrogenation of n-pentane with propene was tested withComplex 11: (p-OK-^(iPr4)PCP)Ir(C₃H₆) immobilized on various solidsupports. The details of the reaction and the results of the runs areset forth in Table 7 and FIG. 3.

Table 7 shows the supported iridium pincer complex has the ability tocatalyze dehydrogenation of pentane with propene at temperatures as lowas 200° C. with unprecedented rates and TONs. While the iridium pincercomplex supported on silica gave about 200 TON in 10 minutes, theiridium pincer complex supported on neutral alumina and florisil,respectively, gave almost full conversion in 10 minutes of 1050 and 830TONs, respectively.

TABLE 7 (p-OK-^(iPr4)PCP)Ir catalyzed gas phase dehydrogenation ofn-pentane [8.7M] under 2 atm of propene “[1.2M]” at 200° C. on varioussolid supports Total Propane mM {%} (E + Z)-1,3- Solid Time Olefins=Double 1-Pentene mM 2-Pentenes mM Pentadienes Entry Support (min) mMbonds^(a) C₃ GC^(b) {Selectivity %}^(c) E- Z- mM 1 Silica 10 205 ± 5 212{17%} 20% 80 ± 2 (40%)  88 ± 1 33 ± 1  7 ± 1 SiO₂ 40  448 ± 22 478 {39%}37% 120 ± 5 (29%)  216 ± 10 84 ± 5 30 ± 2 180 496 ± 8 536 {44%} 40% 91 ±1 (20%) 262 ± 5 104 ± 2  40 ± 1 2 γ-Alumina 10 530 ± 2 584 {48%} 41% 138± 2 (29%) 238 ± 2 100 ± 1  54 ± 2 Al₂O₃ 40  790 878 {70%} 65% 140 (20%)410 150  90 180 1265 1425 {115%} 95% 154 (14%) 673 278 160 3 Basic 10450 ± 5 486 {40%} 42% 127 ± 3 (31%) 205 ± 1 80 ± 2 34 ± 2 Alumina 40 792 ± 25 885 {70%} 65% 138 ± 15 (20%) 410 ± 2 152 ± 15 92 ± 6 Al₂O₃ 1801290 ± 1  1460 {115%} 95% 133 ± 10 (12%)  718 ± 20 272 ± 10 170 ± 5  4Florisil 10 830 ± 2 920 {75%} 75% 124 ± 2 (17%) 440 ± 2 174 ± 1  90 ± 2MgO₃Si 40 1150 ± 40 1273 {103%} 95% 96 ± 4 (10%)  667 ± 15 256 ± 15 125± 5  5 Neutral 10 1050 1190 {97%} 90% 160 (18%) 550 200 140 AluminaAl₂O₃ ^(a)Propane formed = Total dehydrogenation = Total double bondsformed, ^(b)Calculated from ratio of propane to propene as observed byGC, ^(c)Selectivity = (1-pentene/Total monoenes) × 100 s

The transfer dehydrogenation of n-pentane with propene with Complex 11:(p-OK-^(iPr4)PCP)Ir(C₃H₆) immobilized on various solid supports was alsocompared to that of the unsupported complex. The details of the reactionand the results of the runs are set forth in the following Tables 8 and9. Table 8 shows the supported complexes had higher activity compared tothe unsupported complex. Catalyst activity is determined based on rateof reaction, in this case through both TONs and % feedstock consumed. Asshown in Table 8, the TONs and conversions are significantly better forthe supported complexes compared to the unsupported complex.

Table 9 shows the supported complexes also had better recyclabilitycompared to the unsupported complex. In this example, the volatiles(i.e., C5 hydrocarbons) were evacuated and the catalysts were reusedwithout any regeneration treatment.

TABLE 8 Comparison of activity in the unsupported and supported pinceriridium catalyzed gas phase dehydrogenation of n-pentane [8.7M] under 2atm of propene “[1.2M]” at 200° C. Total Propane mM {%} (E + Z)-1,3-Time Olefins =Double 1-Pentene mM 2-Pentenes mM Pentadienes Catalyst(min) mM bonds^(a) C₃ GC^(b) {Selectivity %}^(c) E- Z- mM Complex 10 10 410 ± 11 444 {36%} 36% 153 ± 5 (41%) 148 ± 2  76 ± 1 34 ± 2 Unsupported(Coating on walls) Complex 11 10  225 252 {20%} 22% 75 (33%)  90  36  26Unsupported (Coating on walls) Complex 11 10 530 ± 2 584 {48%} 41% 138 ±2 (29%) 238 ± 2 100 ± 1 54 ± 2 Supported on γ-Alumina Al₂O₃ Complex 1110 830 ± 2 920 {75%} 75% 124 ± 2 (17%) 440 ± 2 174 ± 1 90 ± 2 Supportedon Florisil MgO₃Si Complex 11 10 1050 1190 {97%} 90% 160 (18%) 550 200140 Supported on Neutral Alumina Al₂O₃

TABLE 9 Comparison of recyclability in the unsupported and supportedpincer iridium catalyzed dehydrogenation of n-pentane [8.7M] under 2 atmof propene “[1.2M]” at 200° C. after 10 minutes. Catalyst Time (min)Cycle Total Olefins mM Complex 10 10 First 410 ± 11 Unsupported 10Second 20 (Coating on walls) Complex 11 10 First 450 ± 5  Supported on10 Second 130 Basic-Alumina Al₂O₃ Complex 11 10 First 1050 Supported on10 Second 1100 Neutral Alumina Al₂O₃

Example 7: Dehydrogenation of n-Pentane with Propene Using γ-AluminaSupported Catalyst

As demonstrated in Example 7, it has been found that supported iridiumpincer complex catalyzed dehydrogenation of pentane with propene ispossible at temperatures as low as 160° C.

The transfer dehydrogenation of n-pentane with propene was tested withComplex 11: (p-OK-^(iPr4)PCP)Ir(C₃H₆) immobilized on γ-alumina. Thedetails of the reaction and the results of the runs are set forth inTable 10. The dehydrogenation reaction occurred in the liquid phase at atemperature of only 160° C.

TABLE 10 (p-OK-^(iPr4)PCP)Ir catalyzed liquid phase dehydrogenation ofn-pentane [8.7M] under 2 atm of propene “[1.2M]” at 160° C. Propane mM

%

Catalyst Temp t Total =Double 1-Pentene mM 2-Pentenes mM (E + Z)-1,3- 1mM ° C. min Olefins bonds^(a) C₃ ^(b) {% Fraction}^(c) E- Z- PentadienesComplex 11 160 10 36 ± 2 36 {3%}  3% 8 ± 1 (22%) 20 ± 1  8 ± 1 0

on @ 80 164 ± 2  167 {14%} 15% 14 ± 1 (10%) 108 ± 1  40 ± 1  3 ± 1γ-Alumina 2 atm 180 258 ± 18 270 {22%} 22% 30 ± 2 (12%) 157 ± 10 58 ± 412 ± 1 600 846 ± 5  965 {75%} 65% 105 ± 3 (12%) 445 ± 10 180 ± 4  120 ±2  ^(a)Propane formed = Total dehydrogenation = Total double bondsformed, ^(b)Calculated from ratio of propane to propene as observed byGC, ^(c)Selectivity = (1-pentene/Total monoenes) × 100

indicates data missing or illegible when filedVapor Pressure of pentane at 160° C.=18 atmTotal pressure generated by complete vaporization of 100 μl pentane=24atm

Example 8: Synthesis of C₆H₄(CH₂(^(i)PPr)₂)₂

Dibromo m-xylene (2.00 g, 7.6 mmol) and diisopropylphosphine (1.79 g,15.1 mmol) were dissolved in 15.0 ml acetone in the glove box. Themixture was refluxed under an Ar atmosphere for 24 hours. The reactionmixture was cooled in an ice bath and the dense white precipitate wasseparated by cannula filtration. The white solid was vacuum dried andthen suspended in a mixture of 35.0 ml benzene and triethylamine (4.2ml, 30.2 mmol). The reaction mixture was stirred at rt for 60 h. Theresulting solution was subjected to cannula filtration. The solvent fromthe filtrate was removed under reduced pressure to yield 1.8 g (70%) ofcolorless oil. ³¹P{H} NMR (C6D6, 161.9 MHz): δ 10.19 (s)¹H NMR (C6D6,400 MHz): δ 6.83˜6.92 (m, 4H, aromatic), 1.32 (d of sept, J_(HH)=5.6 Hz,J_(PH)=1.6 Hz, 4H, PCH(CH₃)₂), 0.73 (d, 5.6 Hz, 12H, PCH(CH₃)₂), 0.70(dd, J_(HH)=5.6 Hz, J_(PH)=1.2 Hz, 12H, PCH(CH₃)₂)

Example 9: Synthesis of ^(iPr4)PCPIr(HCl/Br)

Ultra high purity H₂ was bubbled into a 20.0 ml toluene solution of[(COD)IrCl]₂ (1.78 g, 2.6 mmol) and C₆H₄(CH₂(^(i)PPr)₂)₂ (1.80 g, 5.3mmol) for about 15 minutes. The reaction mixture was then stirred at 80°C. under an H₂ atmosphere for 15 h. Solvent was removed from theresulting red solution to yield a red solid. The red solid was thenstirred with 100.0 ml pentane for 30 minutes. The solution was cannulafiltered and filtrate was collected. The extraction was repeated fivemore times and filtrate was collected. Then the residue was furtherstirred with 100 ml pentane overnight and extracted. All filtrate weremixed and the solvent was evaporated to obtain a red solid in 51% yield(1.55 g). NMR analysis indicated the red solid to be 5:1 mixture of^(iPr4)PCPIr(HCl) and ^(iPr4)PCPIr(HBr).

31P NMR (C6D6, 161.9 MHz): δ 58.40 (HBr complex, d, 12.3 Hz), δ 58.44(HCl complex, d, 12.3 Hz)

1H NMR (C6D6, 400 MHz): δ 6.95 (s, 3H, PCP), 2.84 (d of vt, JPH=4.0 Hz,JHH=17.6 Hz, 2H, CH2P), 2.73 (d of vt, JPH=4.4 Hz, JHH=17.6 Hz, 2H,CH2P), 2.71 (m, 2H, PCH(CH3)2), 1.96 (m, 2H, PCH(CH3)2) 1.19 (app. Sext(dqt), 7.7 Hz, 12H, PCH(CH3)2), 0.86˜0.93 (m, 12H, PCH(CH3)2), [−36.25(HCl complex) and −38.25 (HBr complex)] (t, JPH=13.2 Hz, 1H, IrH)

Example 10: Synthesis of Complex 7

Ethylene was bubbled for about 15 minutes into a reddish 60.0 ml pentanesolution of ^(iPr4)PCPIr(HCl/Br) (0.21 g, 0.4 mmol) whereupon thesolution turns colorless. To the above solution 1M LiBEt3H (0.37 ml, 0.4mmol) was added drop wise under ethylene atmosphere. The colorlesssolution then gradually turns brownish. The reaction mixture was stirredovernight under ethylene atmosphere. Removal of pentane from thefiltrate obtained from cannula filtration yields 0.20 g of a brown solidin quantitative yield. NMR and elemental analysis indicate the formationof expected compound in >99% purity. Crystals suitable for X-rayanalysis were grown by slow evaporation of a 10 mg solution of Complex7: (^(iPr4)PCP)Ir(C₂H₄) in 1.0 ml pentane.

31P NMR (C6D6, 161.9 MHz): 51.45

1H NMR (C6D6, 400 MHz): 7.45 7.32 (m, 3H, Arene H), 3.18 (t, J=3.8 Hz,4H, CH2P), 3.11 (t, J=3.0 Hz, 4H, Ir(C2H4)), 2.15 (m, 4H, PCH(CH3)2),1.15 (dd, J=14.7, 7.2 Hz, 12H, PCH(CH3)2), 1.00 (dd, J=13.2, 6.7 Hz,12H, PCH(CH3)2).

Calcd for C22H39IrP2: C, 47.38; H, 7.05; Found: C, 48.23; H, 7.23.

Example 11: Synthesis of Complex 12

Introducing H₂ to a pentane solution of Complex 7: (^(iPr4)PCP)Ir(C₂H₄)into atmosphere results in formation of Complex 12: (^(iPr4)PCP)IrH₄ inquantitative yields as an orange solid.

31P NMR (p-xylene-d10, 161.9 MHz): δ 54.70

1H NMR (p-xylene-d10, 400 MHz): δ 7.02 (s, 3H, PCP), 3.17 (vt, JPH=4.0Hz, 4H, CH2P), 1.55 (m, 4H, PCH(CH3)2), 1.03 (app. qt, 7.5 Hz, 12H,PCH(CH3)2) 0.97 (app. qt, 7.1 Hz, 12H, PCH(CH3)2), −9.40 (t, 10.2 Hz,IrH4)

Example 12: Synthesis of Complex 11

Complex 11: (p-OK-^(iPr4)PCP)Ir(C₃H₆) was synthesized as illustrated inFIG. 4. Synthesized from (p-OMe^(iPr4)PCP)Ir)HCl following a literatureprocedure reported for the synthesis of (p-OK-^(tBu4)POCOP)Ir(C₂H₄) (SeeHuang, Z.; Brookhart, M.; Goldman, A. S.; Kundu S.; Ray, A.; Scott, S.L.; Vicente, B. C.; Adv. Synth. Catal. 2009, 351, 188).

Example 13: Immobilization of Complex 11 onto Solid Supports

A 1 mM stock solution of (p-OK-^(iPr4)PCP)Ir(C₃H₆) was prepared in THF.About 100 μl of this red colored stock solution was transferred tosealable 1.5 ml vials containing 10 mg of solid support. After stirringfor about five minutes the red color of the solution decolorizes and thesolid support turns red in color. THF was evacuated from the vials toobtain a free flow red solid. The vials were refilled with 100 μlpentane. The solution is colorless. The vials were then charged withpropene, flame sealed and subjected to interval free heating by spinningin a rotisserie oven at 200° C.

Example 14: Acceptorless Dehydrogenation of n-Dodecane

Acceptorless dehydrogenation of n-dodecane was accomplished asillustrated in FIG. 5. The complex (_(iPr4)PCP)Ir(C₂H₄) (1.2 mg, 2μmoles) was dissolved in anhydrous degassed n-dodecane (2.0 ml, 9 mmol)in the acceptorless vessel inside a glove box under argon atmosphere.The vessel was then sealed and brought out of the glove box. The vesselwas connected to a Schlenk line and introduced to Argon atmosphere. Thezero time reading was obtained by GC analysis of the reaction mixture.The reaction mixture was then heated at 250° C. by continuously bubblingargon through the system to sparge out the hydrogen that is releasedduring the reaction. The outlet of the gas flow was connected to coldfinger at −15° C. to trap any volatiles. At regular intervals, analiquot was withdrawn from the reactor, and the contents were analyzedby GC. Periodically the contents of the cold finger were also analyzed.

TABLE 11 Acceptorless Dehydrogenation of Pentadecane and Dodecane TimeReaction condition (h) Total Olefins (mM) ^(4iPr)PCP)Ir(C₂H₄) (2.0 mM) +3 28 1 ml dodecane at 250° C. oil bath 6 33 bp = 217° C.(OMe-^(4iPr)PCP)Ir(C₂H₄) (1.0 mM) + 3 15 2 ml dodecane at 220° C. oilbath 6 19 bp = 217° C. 9 22 (OMe-^(4iPr)PCP)Ir(C₂H₄) (1.0 mM) + 1 20 2ml pentadecane at 250° C. oil bath 3 27 (bp = 270° C.)(OMe-^(4iPr)PCP)Ir(C₂H₄) (1.0 mM) + 1 17 2 ml dodecane at 250° C. oilbath 3 33 bp = 217° C. 6 43 (OMe-^(4iPr)PCP)Ir(C₂H₄) (1.0 mM) + 1 62 2ml dodecane at 260° C. oil bath 3 75 bp = 217° C. 6 98(OMe-^(4iPr)PCP)Ir(C₂H₄) (1.0 mM) + 1 32 2 ml dodecane + 3 52 100 mg SiCboiling chips 6 66 at 250° C. oil bath bp = 217° C.

Various modifications and alterations of the process disclosed hereinwill become apparent to those skilled in the art without departing fromthe scope and spirit of the process disclosed herein. Other objects andadvantages will become apparent to those skilled in the art from areview of the preceding description.

A number of patent documents and non-patent documents are cited in theforegoing specification in order to describe the state of the art towhich the process disclosed herein pertains. The entire disclosure ofeach of the cited documents is incorporated by reference herein.

Furthermore, the transitional terms “comprising”, “consistingessentially of” and “consisting of”, when used in the appended claims,in original and amended form, serve to indicate what unrecitedadditional claim elements or steps, if any, are excluded from the scopeof the claim(s). The term “comprising” is intended to be inclusive oropen-ended and does not exclude any additional, unrecited element,method, step or material. The term “consisting of” excludes any element,step or material other than those specified in the claim and, in thelatter instance, impurities ordinarily associated with the specifiedmaterial(s). The term “consisting essentially of” limits the scope of aclaim to the specified elements, steps or material(s) and those that donot materially affect the basic and novel characteristic(s) of theclaimed process. All iridium pincer complex catalysts and methods of usethereof embodied herein can, in alternate embodiments, be morespecifically defined by any of the transitional terms “comprising”,“consisting essentially of” and “consisting of”.

That which is claimed is:
 1. An iridium pincer complex of the formula(^(iPr4)PCP)Ir(C₂H₄).
 2. The iridium pincer complex of claim 1, whereinthe iridium pincer complex is unsupported.
 3. The iridium pincer complexof claim 1, wherein the iridium pincer complex is immobilized on a solidsupport.
 4. An iridium pincer complex of the formula(p-OK-^(iPr4)PCP)Ir(C₃H₆).
 5. The iridium pincer complex of claim 4,wherein the iridium pincer complex is unsupported.
 6. The iridium pincercomplex of claim 4, wherein the iridium pincer complex is immobilized ona solid support.